Lone-pair self-containment in pyritohedron-shaped closed cavities: Optimized hydrothermal synthesis, structure, magnetism and lattice thermal conductivity of Co15F2(TeO3)14
- Authors
- Lü M.; Jiang J.; Zhu B.; Zhao Y.; Zhu T.; Yang H.; Jin Y.; Kabbour H.; Choi K.-Y.; Harrison W.T.A.
- Issue Date
- 21-Feb-2020
- Publisher
- Royal Society of Chemistry
- Citation
- Dalton Transactions, v.49, no.7, pp 2234 - 2243
- Pages
- 10
- Journal Title
- Dalton Transactions
- Volume
- 49
- Number
- 7
- Start Page
- 2234
- End Page
- 2243
- URI
- https://scholarworks.bwise.kr/cau/handle/2019.sw.cau/38009
- DOI
- 10.1039/c9dt04176a
- ISSN
- 1477-9226
1477-9234
- Abstract
- A new oxofluoride Co15F2(TeO3)14 has been prepared by optimized hydrothermal synthesis involving a complex mineralization process. The crystal structure consists of a three-dimensional network of CoO5(O,F) octahedra, distorted CoO5 square pyramids, TeO3 trigonal pyramids and grossly distorted TeO3+3 octahedra, which are linked by sharing corners and edges. The Te(iv) lone pairs are accommodated within novel pyritohedron-shaped [(TeO3)14]28- units. This special framework provides a much larger free space that allows Te atoms to vibrate with a large amplitude, which leads to extremely low lattice thermal conductivity. Magnetic susceptibility data for Co15F2(TeO3)14 show antiferromagnetic ordering below 9.6 K with a substantial orbital component to the effective magnetic moment. An S = 3/2 honeycomb-like spin network was carefully analyzed by experimental techniques and first principles calculations. © 2020 The Royal Society of Chemistry.
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